beta-thiosubstituted acylamino-nitro propiophenones



Unit-6d m-S Pate t fl-THIOSUBSTITUTED ACYLAlVlINO-NITRO PROPIOPHENONESCarlo Giuseppe Alberti and Alberto Vercellone, Milan,

Italy, assignors to some Farmaceutici Italia, a corporation of Italy NoDrawing. Application March '1, 1956 Serial No. 568,709

Claims priority, application Italy March 12, 1955 9 Claims. (Cl. 167-30)This invention relates to newsynthetic products and to the method ofmaking the same. More specifically, the invention relates tonitro-a-acylamino-fl-thio-propiophenones having the general formula N02NH.COR"

wherein R represents alkyl, aminoalkyl, substituted aralkyl, substitutedaryl, and r N05 NH.COR

N0 NH.C OR

wherein R represents alkyl, ,aryl, and dihaloa1kyl,--with a sulfuratedcompound of the type I,

wherein ,R' represents H, alkyl; aminoalkyl, substituted aralkyl, andsubstituted aryl. The two reactants are dissolved in an inert solvent,such as aliphatic and aromatic hydrocarbons, chlorinated hydrocarbons,esters, alcohols and ethers, and are treated at a temperature from 0 to100 C., with or without an alkaline catalyst such as tertiary amines,alkaline alcoholates or alkaline carbonates.

After filtering the reaction mixture, the compounds of formula I areobtained by evaporating the solvent.

The a-acylamino-nitro-acrylophenones used as starting materials in thissynthesis are produced according to US. patent application Serial No.432,034 of May 24, 1954, now abandoned.

The following examples are presented to illustrate the presentinvention, without intending to thereby limit the scope of the appendedclaims.

Example 1 2.34 gr. of p-nitro-a-acetamino-acrylophenone are heated toboiling with 1.46 gr. of mono-thiohydroquinone in 50 cc. of benzene.After boiling for minutes, dissolution occurs and after 30 minutesprecipitation of a crystalline, lightly yellow-colored compoundcommences. Having boiled the reaction mixture for 4 hours, theprecipitate is filtered ofi and washed with benzene; purep-nitro-a-acetamine-B-(p hydroxypheny1 thio)propiophenone is obtained,having a MP. of 168 C. and the formula NH. 0 0C Ha Example 2 2.34 gr. ofp-nitro-a-acetamino-acrylophenone are mixed with 1.34 gr. ofdiethylamino-thioethanol in 50 cc. of benzene and heated to 40 C. whilestirring, in the presence of 0.1 gr. of anhydrous potassium carbonate.After 5 hours, the mixture is filtered and is left standing overnight.Upon evaporating the benzene, an oleous residue is obtained, that iscrystallized from an ethyl ether-petroleum ether mixture. The resultingp-nitro-aacetamino-fi-(Z-diethylaminoethylthio)propiophenone appears inthe form of little white crystals having a MP. of 6061 C. and theformula N 0 CH Example 3 3.03 gr. of p nitro a dichloroacetaminoacrylophenone are heated to boiling with 1.54 gr. o-f thiosalicylic acidin 50 cc. of benzene. After boiling for one hour, the resultingprecipitate is filtered off and recrystallized from ethanol to give purep-nitro-a-dichloroacetaminofl-(Z-arboxylphenylthio)propiophenone whichis obtained in form of small, lightly yellow-colored needles, having aM.P. of -191 C. and the formula (IJOOH NH.COOHO12 Example 4 2.34 gr. ofp-nit-ro-a-acetamino-acrylophenone are heated to boiling with 1.54 gr.of thiosalicylic acid in 50 cc. of benzene. After 4 hours, the resultingprecipitate is filtered off and is recrystallized from ethanol tofurnish pure p nitro cc acetamino ,8 (2 carboxylphenylthio)propiophenonewhich occurs in form of lightly yellow needles, having a M.P. of 187 C.and the formula (E0 OH NH.O OCH;

Example 5 2.34 gr. of p-nitro-a-acetamino-acrylophenone are mixed with0.62 cc. of n-butylrnercaptan in 10 cc. of henzene and stirred at 40 C.for 5 hours in the presence of 0.1 anhydrous potassium carbonate. Themixture is then filtered, and after standing over night, the filtrate isevaporated to dryness. The residue, crystallized from methanol,represents pure p-nitro-a-acetamino-[i-n-butyl thio-propiophenoneappearing in form of small white scales having a M.P. of 106108 C. andthe formula NH-COCHQ Example 6 The foregoing example is repeated, exceptthat, by using p nitro a dichloro acetoamino acrylophenone, p nitro a.dichloroacetoamino 13 n butylthio-propiophenone is obtained in form ofwhite needles,

' Patented Sept. 8, 1959' having a M.P. of 87-88 C. (from methanol), andthe formula.

Non-QC o-prpom-s-omwrwom-on NfLCOCHCl:

Example 7 s NH. 0 011;]: We claim:

1. The fungicidal compounds,para-nitro-alpha-acylamino-beta-thio-propiophenones of the formula:

N110 OR wherein R represents a member of the group consisting ofn-butyl, Z-diethylaminoethyl, p-hydroxyphenyl, 2-carboxylphenyl andNELCOR" and R" represents a member of the group consisting of methyl anddichloro-methyl.

2. The fungicide, 2-p-nitrobenzoyl-2-acetamino-ethylsulfide, having theformula NH.COCHa 2 3. The fungicide,p-nitro-a-acetamino-p-(p-oxyphenylthio)propiophenone, having the formulaNH.COOH

4. The fungicide, p nitro a acetamino ,9 (2- diethylamino ethylthio)propiophenone NELOOCH:

4 5. The fungicide, p nitro a acetamino p -nbutyl-tbio-propiophenone,having the formula NH.CO.CH;

6. The fungicide, p nitro adichloroacetaminofl-n-butyl-thio-propiophenone, having the formula N0.011011 7. The fungicide, p nitro a acetamino p (2-carboxy-phenyl-thio)propiophenone, having the formula COOH l NOQ-Coon-cms N110 0 CH: 8. The fungicide, p nitro a dichloro acetoamino- B (2carboxyl phenyl thio)propiophenone, having the formula NH.C OCHClz 9. Inthe art of combatting fungi, the improvement comprising applying to thelocale of the fungi a fungicidal compound of the formula NH.COR

wherein R represents a member of the group consisting of n-butyl,2-diethylaminoethyl, p-hydroxyphenyl, 2-carboxyphenyl and NHL OR and Rrepresents a member of the group consisting of methyl anddichloro-methyl.

References Cited in the file of this patent UNITED STATES PATENTS FarlowAug. 27, 1946 Long et a1. June 15, 1954 OTHER REFERENCES Farkas et al.:Chemick Listy 48, No. 1-6, pp. 695 705 (1954).

Farkas et al.: Coll. Czech. Chem. Commun., vol. 19, pp. 754-765 (1954).

Farkas et al.: Chem. Absts. 49, col. 9551 (1955).

1. THE FUNGICIDAL COMPOUNDS, PARA-NITROALPHA-ACYLAMINO-BETA-THIO-PROPIOPHENOUS OF THE FORMULA: 